EP1102631B1 - Support de catalyseur a haute selectivite diesel - Google Patents

Support de catalyseur a haute selectivite diesel Download PDF

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Publication number
EP1102631B1
EP1102631B1 EP99941433A EP99941433A EP1102631B1 EP 1102631 B1 EP1102631 B1 EP 1102631B1 EP 99941433 A EP99941433 A EP 99941433A EP 99941433 A EP99941433 A EP 99941433A EP 1102631 B1 EP1102631 B1 EP 1102631B1
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EP
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Prior art keywords
carrier composition
cogel
catalyst
less
total weight
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EP99941433A
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German (de)
English (en)
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EP1102631A1 (fr
Inventor
Jan Nieman
Johannes Wilhelmus Maria Sonnemans
Bas De Kroes
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Akzo Nobel NV
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Akzo Nobel NV
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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/888—Tungsten
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/16—Clays or other mineral silicates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • B01J29/084—Y-type faujasite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • B01J29/16—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J29/166—Y-type faujasite
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
    • C10G11/04—Oxides
    • C10G11/05—Crystalline alumino-silicates, e.g. molecular sieves
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
    • C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used

Definitions

  • the invention relates to a carrier suitable for use in a hydrocracking catalyst that has a high selectivity for middle distillates, in particular diesel, and to a hydrocracking process in which such a catalyst is used.
  • hydrocracking processes to convert hydrocarbonaceous feedstocks into products of a lower boiling range. Such processes entail contacting the feedstock with hydrogen at elevated temperature and pressure under the influence of a catalyst, with the catalyst containing at least a hydrogenation component and an acidic component, the latter effecting the actual cracking.
  • Conventional acidic components include zeolitic acidic components, in particular Y-zeolites, and amorphous acidic components, in particular silica-aluminas.
  • a catalyst suitable for the production of diesel has been described, e.g., in EP 0 540 123.
  • This reference discloses carrier compositions which contain less than 25 wt% of a zeolite Y with a unit cell size below 2.437 nm, more than 25 wt% of a binder selected from alumina, silica, magnesia, titania, clays, zirconia, silica-zirconia, and silica-boria, and at least 30 wt% of a dispersion of silica-alumina in an alumina matrix.
  • a catalyst which comprises nickel and tungsten on a carrier comprising 4 wt% of Y-zeolite, 30 wt% of an alumina binder, and 66 wt% of a silica-alumina.
  • carrier compositions which comprise elemental clay platelets with an average diameter of 1 ⁇ m or less and an average degree of stacking of 20 platelets per stack-or less.
  • the carrier can also contain a matrix material selected from, int. al., amorphous materials such as silica, alumina, silica-alumina, titania and/or zirconia, and optionally, in addition, a zeolite.
  • the carrier composition is used in catalysts suitable for hydroprocessing applications. These catalysts contain the carrier composition as defined above and at least a hydrogenation metal.
  • hydroprocessing in this reference encompasses all processes in which a hydrocarbon feed is reacted with hydrogen at elevated temperature and elevated pressure. These processes include hydrodesulfurisation, hydrodenitrogenation, hydrodemetallisation, hydrodearomatisation, hydroisomerisation, hydrodewaxing, hydrocracking, and hydrocracking under mild pressure conditions, which is commonly referred to as mild hydrocracking.
  • the carrier can also contain a support material selected from, int. al., amorphous materials such as silica, alumina, silica-alumina, titania and/or zirconia, and optionally, in addition, a zeolite. This carrier composition is described as suitable for use in hydroprocessing catalysts in general.
  • the amount of zeolite in the catalysts of both WO 96/07477 and the above-mentioned non-prepublished international patent application, if present at all, is specified to be 3 - 55 wt%, based on the total weight of the catalyst. This corresponds to 3 - 92 wt%, based on the total weight of the carrier composition, if 3 - 40 wt% of hydrogenation metal is present in the catalyst.
  • No catalysts containing both a zeolite and a clay or cogel component, respectively, are disclosed in the Examples of these references. Neither is there any indication of any specific suitability of these cracking components for the production of diesel.
  • the carrier composition of the present invention comprises
  • the carrier composition of the present invention comprises 2 - 20 wt% and more preferably 2 - 12 wt% of the zeolite, based on the total weight of the carrier composition. Further, it is preferred that the carrier composition comprises at least 40 wt% and more preferably at least 50 wt% of the synthetic cracking component, based on the total weight of the carrier composition.
  • the carrier composition additionally comprises an amorphous support material.
  • the day platelets used in the carrier composition of the present invention comprise elemental clay platelets with an average diameter of 1 ⁇ m or less and an average degree of stacking of 20 platelets per stack or less.
  • the average diameter of the clay platelets used in the carrier composition of the present invention is between 1 nm and 0.5 ⁇ m, more preferably in the range of 1 nm to 0.1 ⁇ m, and most preferably in the range of 1 to 50 nm.
  • the average degree of stacking of the clay platelets is preferably not more than 10 platelets per stack, more preferably not more than 5 platelets per stack, and most preferably not more than 3 platelets per stack.
  • the lower limit is constituted by unstacked clay platelets, which have a "degree of stacking" of 1. The two parameters are easily determined by means of transmission electron microscopy.
  • the counter-ions in the interlayer between the clay platelets can be replaced by H 3 O + ions.
  • H 3 O + ions can be introduced into the clay platelets via ion-exchange with, e.g., hydrolysable metal ions or ammonium ions. As will be evident to the skilled person, this can be effected in a manner analogous to that known in the art for the conversion of NaY zeolites into HY zeolites.
  • the clays used in the carrier composition of the present invention may be pillared.
  • the clays used in the carrier composition according to the present invention generally have a B.E.T. surface area in the range of 100 to 1000 m 2 /g, depending on the nature of the metallic elements present in the octahedron layer.
  • the pore volume, determined by means of nitrogen adsorption, is in the range of 0.03 to 1.5 ml/g, again depending on the nature of the metallic elements present in the octahedron layer.
  • the one or more trivalent metallic elements are generally selected from the group of aluminium, borium, gallium, chromium, iron, cobalt, manganese, vanadium, molybdenum, tungsten, indium, rhodium, scandium, or mixtures thereof. They preferably comprise aluminium and more preferably consist essentially of aluminium.
  • the one or more tetravalent metallic elements are generally selected from the group of silicon, titanium, germanium or mixtures thereof. They preferably comprise silicon and more preferably consist essentially of silicon.
  • the one or more divalent metallic elements are generally selected from magnesium, zinc, manganese, copper, beryllium, iron, cobalt, nickel, or mixtures thereof. They preferably comprise and more preferably consist essentially of magnesium.
  • the clay platelets used in the carrier composition of the present invention are preferably saponites.
  • the clay platelets used in the carrier composition of the present invention are those described in WO 96/07477.
  • the cogel used in the carrier composition of the present invention has a saponite content (C A ) of less than 60 %, and the total of sodium and potassium present in the cogel amounts to less than 1 wt%, based on the total weight of the cogel.
  • the cogel must contain less than 1 wt% of the total of sodium and potassium, based on the total weight of the dry cogel.
  • the total of sodium and potassium, based on the total weight of the dry cogel amounts to less than 0.5 wt%, more preferably to less than 0.3 wt%, still more preferably to less than 0.2 wt%, and most preferably to less than 0.1 wt%, based on the total weight of the cogel.
  • the saponite content (C A ) of the cogel contained in the carrier composition of the present invention is less than 60 %.
  • the saponite content (C A ) is less than 55 % and more preferably less than 50 %. It is further preferred that the saponite content (C A ) is at least 10 % and more preferably at least 20%.
  • the saponite content (C B ) is less than 30 %, preferably less than 25 % and more preferably less than 20 %.
  • the saponite contents (C A ) and (C B ) are determined by method A and B respectively, as defined in WO 00/00286.
  • the cogel contained in the carrier composition of the present invention is essentially X-ray amorphous.
  • X-ray amorphous is well-known to the person skilled in the art and means that no crystalline peaks are contained in a spectrum but only broad amorphous peaks are observed.
  • essentially X-ray amorphous in the sense of the present invention means that apart from any saponite peaks, there are essentially no further crystalline peaks visible in the X-ray diffraction pattern of the cogel.
  • Saponite peaks generally include crystalline peaks located at 20°(2 ⁇ ), 35°(2 ⁇ ), and 60°(2 ⁇ ), and optionally 28°(2 ⁇ ).
  • the cogel which is contained in the carrier composition of the present invention has a B.E.T. surface area of at least 400 m 2 /g. More preferably, the B.E.T. surface area of the cogel is at least 450 m 2 /g and most preferably it is at least 500 m 2 /g.
  • the surface area is determined as described in the above-mentioned non-prepublished international patent application and if not mentioned otherwise is the surface area of an uncalcined sample.
  • the surface area of the cogel does not decrease dramatically when exposed to high temperatures. More in particular, it is preferred that the quotient between the surface area of the cogel after calcination in air at 550°C for one hour and the surface area of the uncalcined cogel is at least 0.80. It is further preferred that the surface area of the cogel after calcination in air at 550°C for one hour is at least 350 m 2 /g and more preferably at least 400 m 2 /g.
  • the cogel contained in the carrier composition of the present invention has a cation-exchange capacity of at least 0.5 wt%, more preferably of at least 1.0 wt%, and most preferably of at least 2.0 wt%, based on the total weight of the cagel.
  • the cation-exchange capacity of the cogel is less than 10 wt%, based on the total weight of the cogel.
  • the cation exchange capacity is determined as defined in WO 00/00286.
  • the cation-exchange capacity of the cogel should not dramatically decrease when high temperatures are applied, e.g., during calcination or use. Therefore, it is preferred that the quotient between the cation-exchange capacity of the cogel after calcination in air at 550°C for one hour and the cation-exchange capacity of the uncalcined cogel is at least 0.6 and more preferably at least 0.7. Furthermore, it is preferred that the cation-exchange capacity of a sample calcined in air for one hour at 550°C is at least 0.5 wt%, more preferably at least 1.0 wt% and most preferably at least 2.0 wt%.
  • the di-, tri-, and tetravalent metallic elements are generally selected from those mentioned above for the clay platelets.
  • the trivalent metallic element preferably comprises and more preferably consists essentially of aluminium.
  • the tetravalent metallic element preferably comprises and more preferably consists essentially of silicon.
  • the divalent metallic elements are preferably selected from non-Group VIII metallic elements such as, preferably, magnesium, zinc, manganese, copper, beryllium, or mixtures thereof, optionally in combination with one or more Group VIII non-noble metallic elements.
  • Preferred Group VIII non-noble metallic elements are cobalt or nickel or mixtures thereof.
  • the non-Group VIII metallic element preferably comprises magnesium and more preferably consists essentially of magnesium.
  • the carrier composition of the present invention contains both clay platelets and a cogel
  • the di-, tri-, and tetravalent metallic elements may be the same or different in both the clay platelets and the cogel.
  • the molar ratio between the oxidic compounds of the tetravalent metallic elements and the oxidic compounds of the trivalent metallic elements of the cogel generally is at least 2 and not more than 30. Preferred are molar ratios of at least 4, even more preferably of at least 6. It is further preferred that the molar ratio is not more than 20, more preferably not more than 12.
  • the atomic ratio between the one or more divalent metallic elements and the total of tri- and tetravalent metallic elements contained in the cogel lies between 0.03 and 1.00. It is preferred that this atomic ratio lies between 0.10 and 1.00 and more preferably between 0.20 and 0.50.
  • the values given for the molar and atomic ratios are the ratios in the final cogel and can be determined from the final product by methods known in the art.
  • the cogel used in the carrier composition of the present invention is that described in the above-mentioned non-prepublished intemational patent application.
  • the zeolite used in the carrier composition of the present invention is a Y-type zeolite having a unit cell size below 24.35 ⁇ .
  • the zeolite has a unit cell size between 24.20 ⁇ and 24.35 ⁇ , and more preferably between 24.25 ⁇ and 24.35 ⁇ .
  • the zeolite will generally contain less than 0.5 wt% of alkali metal oxide and preferably less than 0.2 wt%, based on the total weight of the zeolite.
  • the molar ratio between the silicon and the aluminium contained in the zeolite preferably lies between 3.5 and 100 and more preferably between 12 and 100.
  • Suitable zeolites are commercially available from, e.g., Zeolyst or Tosoh.
  • the carrier composition may comprise an amorphous support material, e.g., alumina, silica, zirconia, titania, or mixtures of these materials.
  • the support material comprises and more preferably consists essentially of alumina.
  • the catalyst according to the invention comprises the carrier composition of the present invention and at least one hydrogenation metal component, with the hydrogenation metal being selected from the Periodic Table's Group VIB or Group VIII metals, or mixtures thereof.
  • the word "component” in this context denotes the metallic form of the metal, its oxide form, or its sulfide form, or any intermediate, depending on the situation.
  • the hydrogenation metal is selected from one or more noble Group VIII metals or a combination of one or more Group VIB and one or more non-noble Group VIII metals. Even more preferably, a combination of molybdenum or tungsten with nickel or cobalt is employed as hydrogenation metal, most preferably a combination of tungsten with nickel.
  • the catalyst generally contains 0.05 - 5 wt% of the one or more noble Group VIII metals, calculated as metal, based on the total weight of the catalyst. If, on the other hand, the hydrogenation metal is selected from a combination of one or more Group VIB and one or more non-noble Group VIII metals, the catalyst generally contains 2 - 40 wt% of the one or more Group VIB metals, calculated as trioxide, and 1 - 10 wt% of the one or more non-noble Group VIII metals, calculated as oxide, based on the total weight of the catalyst.
  • the catalyst can further contain other components such as phosphorus.
  • phosphorus can be incorporated into the catalyst in a suitable manner by contacting the catalyst during any one of its formative stages with an appropriate quantity of a phosphorus-containing compound, e.g., phosphoric acid.
  • the catalyst can be impregnated with an impregnating solution comprising phosphorus in addition to any other components. If the catalyst according to the invention contains phosphorus, this compound is preferably present in an amount of 0.5 - 10 wt%, calculated as P 2 O 5 , based on the total weight of the catalyst.
  • the catalyst according to the invention generally has a B.E.T. surface area in the range of 50 to 600 m 2 /g, preferably in the range of 100 to 400 m 2 /g (after calcination).
  • the catalyst of the present invention can be prepared by processes known in the art, e.g., according to the following procedure:
  • zeolite, amorphous support material, and the synthetic cracking component are mixed. This can be done in several ways: it is, e.g., possible to first mix the amorphous support material and the zeolite, followed by mixing of the synthetic cracking component with the mixture of amorphous support material and zeolite. However, it is also possible to first mix the amorphous support material and the synthetic cracking component, followed by mixing of the zeolite with the mixture of amorphous support material and synthetic cracking component. Finally, it is also possible to add the amorphous support material, the synthetic cracking component, and the zeolite to a vessel and mix all three compounds simultaneously.
  • the mixture is shaped into particles, e.g., by extrusion.
  • the metal components can, e.g., be incorporated into the catalyst composition by impregnating the shaped particles, optionally after intermediate calcination, with an impregnating solution containing precursors of the hydrogenation metal components to be introduced, optionally in combination with other components such as phosphoric acid and/or complexing agents known in the art.
  • the metals-containing particles may be subjected to a final calcination for a period of, e.g., 0.1 to 10 hours at a temperature of generally 350° - 900°C, preferably of 400° - 800°C.
  • the catalyst particles may have many different shapes.
  • the suitable shapes generally include spheres, cylinders, rings, and symmetric or asymmetric polylobes, for instance tri- and quadrulobes.
  • the particles usually have a diameter in the range of 0.5 to 10 mm, and their length likewise is in the range of 0.5 to 10 mm.
  • the catalyst contains non-noble Group VIII metals and/or Group VIB metals as hydrogenation metals, it is preferably sulfided prior to use. This may be done in an otherwise conventional manner, say, by contacting the catalyst in the reactor at increasing temperature with hydrogen and a sulfur-containing feed, or with a mixture of hydrogen and hydrogen sulfide. If the catalyst contains a noble Group VIII metal, there is no need for sulfiding as a rule, and a reducing step, e.g. with hydrogen, will suffice.
  • the catalyst according to the invention is particularly suitable for use in a process for converting heavy feedstock into middle distillates, in particular diesel, which process comprises contacting the feedstock at elevated temperature and pressure with hydrogen in the presence of the catalyst of the present invention.
  • the process of the present invention is carried out at the following process conditions: temperature in the range of 300° to 450°C hydrogen pressure in the range of 25 to 200 bar space velocity in the range of 0.2 to 5 kg feed per litre catalyst per hour (kg/l/h) H 2 /oil ratio in the range of 250 to 2000 NI/I
  • the conditions selected are such as will give a conversion of at least 70 wt%.
  • conversion in this context refers to the weight, in per cent, of obtained product with a boiling point below 360°C vis-à-vis the weight of the feedstock deployed.
  • Suitable feedstocks for the process of the present invention are, e.g., gas oils, deasphalted oils, coker gas oils, and other thermally cracked gas oils and syncrudes, optionally originating from tar sands, shape oils, residue upgrading processes, or biomass. Combinations of various feedstocks can be applied.
  • part or all of the feedstock can be subjected to a hydrotreatment prior to hydrocracking to remove sulfur- and/or nitrogen-containing compounds from the feedstock.
  • a hydrotreatment prior to hydrocracking to remove sulfur- and/or nitrogen-containing compounds from the feedstock.
  • Use can be made, e.g., of two reaction zones arranged in series, with at least part and preferably the entire effluent from the first reaction zone where the hydrotreating step is performed being passed to the second reaction zone where the hydrocracking occurs.
  • the first reaction zone comprises, e.g., a conventional hydrotreating catalyst which, e.g., contains at least one Group VIB and/or at least one Group VIII metal component on an amorphous support, e.g., an alumina support.
  • the second reaction zone preferably comprises the catalyst composition of the present invention.
  • the present invention is illustrated by the following Examples.
  • Example 1 (Catalyst according to the invention)
  • Alumina was peptised by mixing it with some HNO 3 and water. Then the alumina, a zeolite commercially available from Zeolyst under the designation CBV-720 (unit cell size: 24.30 ⁇ , silica/alumina molar ratio (SAR): 30), and the ammonium-exchanged cogel were added in such amounts as to obtain a mixture comprising 10 wt% of the zeolite, 60 wt% of the cogel, and 30 wt% of the alumina. The mixture was kneaded until an extrudable dough was formed. The mixture was then extruded, and the resulting 1.5 mm cylindrical extrudates were dried overnight at 120°C and subsequently calcined for 1 hour at a temperature of 550°C.
  • CBV-720 unit cell size: 24.30 ⁇ , silica/alumina molar ratio (SAR): 30
  • SAR silica/alumina molar ratio
  • the extrudates were impregnated with an aqueous solution of Ni(NO 3 ) 2 ⁇ 6H 2 O and ammonium tungstate.
  • the sample was subsequently dried at a temperature of 120°C and calcined at a temperature of 480°C during one hour.
  • a saponite was prepared as described in Example 7 of WO 96/07613.
  • the resulting mixture was stirred for 45 minutes at 50°C.
  • the mixture was then dewatered and the whole procedure was repeated once again.
  • the filter cake was then washed thoroughly with demineralised water until no chloride could be detected anymore using a silver nitrate solution. Finally the filter cake was dried overnight at 120°C.
  • the saponite had the following characteristics: amount of the total of Na and K 0.04 wt% molar silica alumina ratio 11.8 atomic ratio between magnesium and the sum of silicon and aluminium 0.44
  • Example 2 The alumina and the zeolite described in Example 1 and the ammonium-exchanged saponite were added in such amounts as to obtain a mixture comprising 10 wt% of the zeolite, 60 wt% of the saponite, and 30 wt% of the alumina. The mixture was then treated, impregnated, and calcined as described in Example 1.
  • silica-alumina had the following properties: amount of the total of Na and K 0.07 wt% molar silica alumina ratio 4.2 atomic ratio between magnesium and the sum of silicon and aluminium 0
  • Example 2 The alumina and the zeolite described in Example 1 and the conventional silica-alumina were added in such amounts as to obtain a mixture comprising 10 wt% of the zeolite, 60 wt% of the silica-alumina, and 30 wt% of the alumina. The mixture was then treated, impregnated, and calcined as described in Example 1.
  • the catalysts were presulphided by heating for 4 hours in a 10 vol% H 2 S / 90 vol% H 2 gas stream at 385°C and atmospheric pressure.
  • the presulphided catalysts were then tested in hydrocracking involving a hydrotreated heavy vacuum gas oil.
  • the hydrotreated heavy vacuum gas oil had an initial sulphur content of 189 ppm and an initial nitrogen content of 33 ppm.
  • it was spiked with dimethyldisulphide and t-butylamine until a sulphur content of 2 wt% and a nitrogen content of 1000 ppm was reached.
  • the further characteristics of the hydrotreated vacuum gas oil were as follows: initial boiling point 106 °C 5 wt% 248 °C 10 wt% 297 °C 20 wt% 346 °C 30 wt% 378 °C 40 wt% 403 °C 50 wt% 424 °C 60 wt% 442 °C 70 wt% 464 °C 80 wt% 488 °C 90 wt% 517 °C 95 wt% 540 °C final boiling point 599 °C
  • the required operating temperature (ROT) and the diesel selectivity (defined as the weight fraction with a cut point of 260°C - 360°C, based on the total weight of fresh feed) were determined for a conversion of 70%.
  • conversion in this context refers to the weight, in percent, of obtained product with a boiling point below 360°C vis-à-vis the weight of the feedstock deployed.
  • the determination of the diesel selectivity and the ROT are well within the scope of the skilled person.
  • ROT (°C) diesel selectivity (wt%) Example 1 393.0 22.5

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Claims (8)

  1. Composition de support comprenant
    a) au moins 40 % en poids, par rapport au poids total de la composition de support, d'un composant de craquage synthétique, qui comprend des composés oxydes d'un ou plusieurs éléments métalliques trivalents, éléments métalliques tétravalents et éléments métalliques divalents, ledit composant de craquage synthétique étant choisi parmi des plaquettes d'argile élémentaire avec un diamètre moyen de 1 µm ou moins et un degré moyen d'empilement de 20 plaquettes par pile ou moins, et/ou un cogel avec une teneur en saponite (CA) de moins de 60 %, dans lequel le total de sodium et de potassium s'élève à moins de 1 % en poids, par rapport au poids total du cogel, et
    b) de 1 à 25 % en poids, par rapport au poids total de la composition de support, d'une zéolite Y avec une taille de motif élémentaire comprise entre 24,20 et 24,35 Å.
  2. Composition de support selon la revendication 1, dans laquelle l'argile dont sont formées les plaquettes d'argile est une saponite.
  3. Composition de support selon la revendication 1 ou 2, dans laquelle le cogel comprend des composés oxydes d'aluminium, de silicium et de magnésium.
  4. Composition de support selon les revendications 1 à 3, dans laquelle la composition de support comprend un matériau de support amorphe.
  5. Composition de support selon la revendication 4, dans laquelle le matériau de support amorphe comprend de l'alumine.
  6. Catalyseur comprenant la composition de support selon les revendications 1 à 5, et au moins un composant métallique d'hydrogénation choisi parmi les composants possédant un métal du Groupe VIB, les composants possédant un métal du Groupe VIII ou leurs mélanges.
  7. Catalyseur selon la revendication 6, dans lequel le composant métallique d'hydrogénation comprend une combinaison de composants de tungstène et de nickel.
  8. Procédé de conversion de matière première lourde en distillats moyens, comprenant une mise en contact de la matière première avec de l'hydrogène à des température et pression élevées et en présence du catalyseur selon les revendications 6 ou 7.
EP99941433A 1998-08-05 1999-07-15 Support de catalyseur a haute selectivite diesel Expired - Lifetime EP1102631B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP99941433A EP1102631B1 (fr) 1998-08-05 1999-07-15 Support de catalyseur a haute selectivite diesel

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
EP98202635 1998-08-05
EP98202635 1998-08-05
PCT/EP1999/005049 WO2000007723A1 (fr) 1998-08-05 1999-07-15 Support de catalyseur a haute selectivite diesel
EP99941433A EP1102631B1 (fr) 1998-08-05 1999-07-15 Support de catalyseur a haute selectivite diesel

Publications (2)

Publication Number Publication Date
EP1102631A1 EP1102631A1 (fr) 2001-05-30
EP1102631B1 true EP1102631B1 (fr) 2004-03-10

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EP99941433A Expired - Lifetime EP1102631B1 (fr) 1998-08-05 1999-07-15 Support de catalyseur a haute selectivite diesel

Country Status (11)

Country Link
US (1) US6716337B2 (fr)
EP (1) EP1102631B1 (fr)
JP (1) JP2002522200A (fr)
KR (1) KR100595120B1 (fr)
CN (1) CN1154539C (fr)
AT (1) ATE261340T1 (fr)
AU (1) AU5505599A (fr)
CA (1) CA2339379C (fr)
DE (1) DE69915492D1 (fr)
DK (1) DK1102631T3 (fr)
WO (1) WO2000007723A1 (fr)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7824540B2 (en) * 2004-06-22 2010-11-02 Albemarle Corporation Process for upgrading liquid hydrocarbon feeds
US20120022305A1 (en) * 2007-07-16 2012-01-26 Conocophillips Company Hydrocracking process for making renewable diesel from oils and/or fats
US8652447B2 (en) * 2008-12-18 2014-02-18 Chevron U.S.A. Inc. Cosmetic and personal care products containing synthetic magnesium alumino-silicate clays
GB0909527D0 (en) * 2009-06-03 2009-07-15 Univ Manchester Modified zeolites and their use in the recycling of plastics waste

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3951864A (en) * 1972-12-11 1976-04-20 Chevron Research Company Hydrocarbon conversion catalyst
GB8619151D0 (en) * 1986-08-06 1986-09-17 Unilever Plc Catalyst base
US4810369A (en) * 1987-05-07 1989-03-07 Union Oil Company Of California Process for the catalytic cracking of feedstocks containing high levels of nitrogen
TW252053B (fr) * 1991-11-01 1995-07-21 Shell Internat Res Schappej Bv
EP0778792A1 (fr) * 1994-09-02 1997-06-18 Akzo Nobel N.V. Catalyseur comprenant au moins un composant metallique d'hydrogenation et une argile synthetique
JP2002519275A (ja) 1998-06-29 2002-07-02 アクゾ ノーベル ナムローゼ フェンノートシャップ ４価、３価および２価の金属元素の酸化化合物を含むコゲル

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KR20010079600A (ko) 2001-08-22
US20020179490A1 (en) 2002-12-05
DK1102631T3 (da) 2004-07-12
JP2002522200A (ja) 2002-07-23
WO2000007723A1 (fr) 2000-02-17
CA2339379C (fr) 2008-12-23
ATE261340T1 (de) 2004-03-15
CN1154539C (zh) 2004-06-23
AU5505599A (en) 2000-02-28
KR100595120B1 (ko) 2006-07-03
US6716337B2 (en) 2004-04-06
DE69915492D1 (de) 2004-04-15
CA2339379A1 (fr) 2000-02-17
EP1102631A1 (fr) 2001-05-30
CN1316921A (zh) 2001-10-10

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